Method of controlling fungi with organic sulfur ester compounds



United States Patent My invention relates to esters of an. organic aliphatic or aromatic acid with an alkyl xanthoyl carbinol or with a dialkyl-dithiocarbamyl carbinol.

This is a division of Serial No. 161,245, filed December 21, 1961, which in turn is a continuation-in-part of U.S. application Serial No. 827,692, filed July 17, 1959,

now Patent No. 3,126,405, granted March 24, 1964,

which relates to organic sulfur compounds havingthe formula:

in which R is a methoxy, ethoxy, isopropyloxy or a dimethylamino or diethylamino group and R is a methyl or phenyl group; and to a process for preparing these compounds, characterized in that either a metal alkylxanthate having the formula:

R O l(l1SMe in which R is preferably methyl, ethyl or isopropyl, and Me is a metallic element (e.g. sodium or potassium) or a metal dialkyl d-ithiocarbamate having the formula:

/NCSM6 R S in which R is methyl or ethyl and Me is sodium or potassium, is reacted with a chloromethyl ester of a carboxylic acid, such as acetic or benzoic acid, of the formula:

R COOCH Cl in which R is methyl or phenyl. The above-mentioned copending application also relates to fungicidal composi- 'tions comprising substances of the aforementioned type.

I have found that compounds having the Formula 1, in which R has the aforementioned meaning and R isa benzyl group (CH C H have a high fungicidal ac tivity.

Objects of my application comprise compounds having the Formula 1 in which R has the above-mentioned meaning and R is a benzyl group, a process for preparing them and the fungicidal compositions containing one or more of said compounds, alone or in admixture with other active and/ or auxiliary substance.

The compounds of my invention are obtained by reacting chloromethylphenylacetate with a metal compound having the formula:

in which R has the aforementioned meaning and Me is an alkali metal, such as sodium or potassium according to the equation:

"ice

The reaction is carried out in the presence of an inert solvent capable of dissolving one or both reactants. As solvents, monohydric alcohol, ketones or their mixtures may be used. Suitable temperatures may vary within fairly wide limits, e.g. from 10 to C. The duration of the reaction varies from 1 to 16 hours. It is convenient, sometimes, to use an excess of one of the two reagents over the stoichiometric amount.

The metal halide formed as a byproduct of the reaction can be eliminated by filtering or by adding Water. In the latter case, the inorganic salt and the excess, if any, of organic salt are dissolved, thereby resulting in the simultaneous precipitation of the desired product. The main reaction product can also be isolated by other known methods such as concentration, distillation and crystallization. The following illustrating examples are given to better illustrate the preparation of the materials, and are not meant to limit the scope of the invention.

EXAMPLE 1 18.4 g. of chloromethyl phenylacetate are added to a suspension of 15.7 g. of sodium dimethyldithiocarbamate in 80 cc. of acetone. An exothermic reaction takes place,"

with precipitation of sodium chloride. The mixture is refluxed for half an hour and is then left to stand for 15 hours. The reaction mixture is then poured into 500 cc.

of Water; the precipitate thus formed is filtered undervacuum and Washed with water. 26 g. of dimethyl dithiovcarbamylcarbinol phenylacetate, having the formula EXAMPLE 2 18.4 g. of chloromethyl phenylacetate are added to a suspension of 19.2 g. of potassium ethylxanthate in cc. of acetone; an exothermic reaction takes place, with precipitation of potassium chloride. The mixture is refluxed for half an hour and is then left to stand for 15 hours. The reaction mixture is then poured into 150 cc. of H 0; the oil thus separated is treated with 70 cc; of methylene chloride and washed twice with H O (each time 50 cc.). After drying on CaCl and removing the solvent by reduced pressure, 21 g. of ethylxanthoylcarbinol phenylacetate, having the formula:

fluxed for half an hour and is then left to stand for 15 7 hours. The reaction mixture is then poured into 15 0 cc. of water; the oil thus separated is treated with 70 cc. of methylene chloride and washed twice with H 0 (50 cc. each time)-. After drying on CaCl and evaporation of 1) the solvent under reduced pressure, 28 g. of diethyl dithio carbamyl-carbinol phenylacetate, having the formula:

CgHs

are obtained as a slightly turbid oil having:

D =1.167; n =1.586O

N calculated=4.7l%; N found=4.7l4.69%.

Formulations containing the compounds of the instant invention to be used as fungicides can, for example, have the following compositions:

(1) 90 g. of dimethyl dithiocarbamylcarbinol phenylacetate, 6.8 g. of lignin sulphite, 3 g. of expanded silica, 0.15 g. of kieselguhr, and 0.05 g. of wetting agent obtained by condensation of ethylene oxide;

(2) 50 g. of diethyl dithiocarbamylcarbinol phenylacetate, 40 g. of kieselguhr, 2 g. of expanded silica and 8 g. of lignin sulphite.

In application, the aforementioned formulations are added to water in such amounts as to reach the desired concentration. A homogeneous dispersion, ready for use (nebulization of plants) is then obtained by simple mechanical agitation.

Evaluation of the anti-oidial activity.The method used for evaluating anti-oidial activity consists of nebulizing under standard conditions aqueous dispersions of the products to be tested on small tobacco plants of the Virginia Bright variety bred under standard conditions. When the nebulized product deposited thereon has become completely dry, the test plants are infected by slight rubbing with leaves covered with Oidium (Erysiphe cichoracearum). The determination of the infection is carried out by estimating the percent proportion of leaf surface area covered with Oidium about 15 days after treatment and by comparing it with the infection of untreated controls. The following classes of degrees of intensity of infection were thus established, in increasing order of infection:

(1) No infection (2) Considerable reduction of infection as compared with the untreated control (-20% against 70-90%) (3) Evident reduction of infection as compared with the untreated control (-40% against 70-90%) (4) Slight reduction of infection as compared with the untreated control (-60% against -90%) (5 Infection as in the untreated control A sample of commercial colloidal sulfur was used as reference of comparison.

Intensity of infection after 15 days Product Dose,

percent Dimethyldithiocarbamylcarbinol plienylace- 0. 250

tote

Ditetthyl dithiocarbamylcarbinol phenylac ei 0. 0500 ceme-uwmwwmtoi- 0. 0500 Colloidal sulfur 0. 0250 The fungicidal activity of the products according to the invention is illustrated by the following results obtained by standard laboratory methods.

By this technique, small filter paper disks with 1 cm. diameter, impregnated with the solutions of the products under examination, are placed on the agar-agar coated surface of Petri dishes seeded with test fungi. After incubation for 72 hours, the haloes of inhibition of fungine growth around those disks are determined, and expressed in mm. The known fungicide sodium pentachlorophenate was taken as a reference for comparison.

The results are classified as follows:

O-inhibition halo with diameter less than 1 mm. 1-inhibition halo with diameter less than 1-2 mm. 2-inhibition halo with diameter less than 3-4 mm. 3inhibition halo with diameter less than 5-7 mm. 4-inhibition halo with diameter less than 8-11 mm. 5-inhibition halo with diameter less than 12-15 mm. 6-inhibition halo with diameter less than 16-20 mm. 7-inhibition halo with diameter less than 21-25 mm. 8inhibition halo with diameter greater than 25 mm.

Table 2 Dose, Alter- Asper- Pm- Sacc. Product percent naria gillus icill. ell.

tcnuis m'ger roquef.

Dimethyldithiocarbamyl-carbinol 1 4 4 2 2 phcnylacetate. 0. 2 4 4 2 2 Ethylxanthoylcar- 0. 04 1 1 0 0 binol phenylaee- 1 3 2 2 1 tate 0. 2 3 2' 1 1 0. 04 0 0 0 0 Dicthyldithiocarbamyl-carbinol 1 4 0 1 U phenylaeetate 0.2 3 0 1 0 0. 04 2 O 0 0 Sodium penta- 1 7 6 7 5 ehloro-phenate 0. 2 5 5 5 2 0. 04 2 1 2 1 (1)) EVALUATION OF THE CAPACITY OF THE PROD- UCTS TO INHIBIT GROWTH AND DIFFUSION OF FUNGINE MYCELIUM ACCORDING TO THE PORCE- LAIN CUP METHOD The cup method differs from the aforementioned method only in the use of a procelain cup containing a constant dose of solution of the product to be examined, in lieu of small paper disks. Sodium pentachlorophenate was taken as a reference for comparison.

The results obtained are classified by indexes as hereinbefore defined.

Table 3 Dose, Alter- Aspar- Pm- Sacc. Product percent naria gillus kill. all.

tennis niger rogue].

Dim cthyldithiocarbaniyl-carbinol 1 6 4 3 3 phenylacetate. 0. 2 6 4 1 2 0. 04 2 1 0 0 Ethylxanthoylcarbinolphenyl- 1 4 4 2 1 acetate 3 3 1 0 0. 04 1 1 0 0 Diethyldithiocarbamykcarbinol 1 4 2 3 0 phenylacetate. 0. 2 3. 1 1 0 0. 04 2 0 0 0 Sodium penta- 1 7 6 6 5 chlorophenate. 0. 2 6 5 5 2 0. 04 2 1 2 1 (0) EVALUATION OF THE CAPACITY TO INHIBIT GER- MINATION AND GROWTH OF FUNGINE MYCELIUM, OF THE PRODUCTS INCORPORATED IN THE NUTRI- TIVE AGAR'AGAR (STREAK METHOD) The streak method allows the examination of products hardly diffusible in solid agar-agar. By this method, the solution of the products is incorporated in the nutritive substrate, while the inoculation of the test fungus is carried out by means of streaks with suspension of spores The reading of the plates is carried out after 72 hours and the growth of the fungi is evaluated by indexes defined as follows:

no difference in respect of water as a control 1slight difference in respect of water as a control 2-colonies spread over all streaks 3some colonies on some streaks 4-no fungus growth Table 4 Dose, Alter- Asper- Pen- Sacc. Product percent naria gillus icill. ell.

team's m'ger roquef.

Dimethyldithiocarbemyl-carbinol 0.2 4 8 1 0 phenylaeetate 0. 04 3 2 0 0 0.008 2 1 0 0 Ethylxanthoylcarbinol-phenylace- 0. 2 4 3 4 2 tate 0. 04 4 3 3 1 0 008 2 1 0 0 Diethyldithiocarbamyl-carbinol- 0. 2 2 l 2 0 phenylacetate 0. 04 1 1 1 0 0. (108 1 0 0 0 Sodium penta 0.2 4 4 4 4 ehloro-phenate... O. 04 4 4 4 4 0. 008 4 2 2 1 ((1) EVALUATION OF THE CAPACITY TO INHIBIT SUNDRY FUNGUS GROWTHS An aqueous dispersion of formulation 1 above was applied by nebulation under standard conditions on young kidney beans plants grown in part under artificial light, after drying of the fungicide film on the plants, the plants were infected with bean rust (Uromyces appendiculatus). A 0.1% aqueous dispersion of diethyldithiocarbamyl carbinol phenylacetate inhibited the infection, While a 0.25% aqueous dispersion of dimethyldithiocarbamyl phenylacetate reduced the same infection to 2%, as compared with that of the untreated controls.

A 0.0125 aqueous dispersion of diethyldithiocarbamyl carbinol acetate, applied by nebulation under standard conditions on grapevine leaves placed in a Petri dish, inhibited the development of downy mildew (Plasmopara viticola) to 5% of that of the untreated controls.

A 0.5% aqueous dispersion of the same product, nebulized under standard conditions on broad bean leaves in Petri dishes, reduced to 5%, as compared to the untreated controls, the infection of chocolate spot on broad bean (Botrytis fabae), which was seeded after complete drying of the product deposited on the leaves.

A 0.025% aqueous dispersion of the above product, deposited dropwise on glass slides, inhibited the germination of Alternaria tenuis spores.

I claim:

1. A fungicidal composition, comprising an organic sulfur compound having the formula:

in which R is selected from the group consisting of methoxy, ethoxy, isopropoxy, dimethylamino and diethylamino, and R is benzyl, a carrier and a surfactant.

2. The method of controlling fungi on plants, which comprises applying, to the plants, the fungicide dimethyldithiocarbamylcarbinol phenylacetate.

3. The method of controlling fungi on plants, which comprises applying, to the plants, the fungicide ethyl- Xanthoylcarbinol phenylacetate.

4. The method of controlling fungi on plants, which comprises applying, to the plants, the fungicide diethyldithiocarbamylcarbinol phenylacetate.

References Cited by the Examiner UNITED STATES PATENTS 2,907,786 10/59 Gundel 260-455 2,910,497 10/59 Meuly 250455 2,943,972 7/60 Van der Kerk 167-22 2,990,317 6/ 61 Jones et a1. 16722 JULIAN S. LEVITT, Primary Examiner.

LEWIS GOTTS, Examiner. 

1. A FUNGICIDAL COMPOSITION, COMPRISING A ORGANIC SULFUR COMPOUND HAVING THE FORMULA: 